Repozytorium

Isomerisation and controlled condensation in an aqueous medium of allyl alcohol catalysed by new water-soluble rhodium complexes with 1,3,5-triaza-7-phosphaadamantane(PTA).

Autorzy

Piotr Smoleński

Marina V. Kirillova

Silva M. Fátima. C. Guedes da

Armando J. L. Pombeiro

Rok wydania

2013

Czasopismo

Dalton Transactions

Numer woluminu

42

Strony

10867-10874

DOI

10.1039/c3dt50992c

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

New aqua-soluble rhodium(I) [Rh(CO)(PTA)4]Cl (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) and rhodium(III) [RhCl2(PTA)4]Cl (2) complexes have been synthesized via the reaction of [{Rh(CO)2(μ-Cl)}2] or RhCl3·3H2O, respectively, with stoichiometric amounts of PTA in ethanol. Compound 1 is also obtained upon reduction of 2 in an H2/CO atmosphere. They have been characterized by IR, 1 H and 31P{H} NMR spectroscopies, elemental and single crystal X-ray diffraction analyses. While compound 1 shows distorted square-pyramid geometry (τ5 = 0.09) with a P3C-type basal plane, compound 2 is octahedral with the chloro ligands in the cis position. The hydride rhodium(I) complex [RhH(PTA)4] (3) is formed upon the addition of NaBH4 to an aqueous solution of 1 or 2. Compounds 1–3 (in the case of 2 upon reduction by H2) act as homogeneous catalysts, or catalyst precursors, in the isomerisation and condensation of allyl alcohol at room temperature and in an aqueous medium. The product selectivity is easily controlled by changing the concentration of the base in the reaction mixture, thus resulting in the exclusive formation of either 3-hydroxy-2-methylpentanal (HP) or 2-methyl-2-pentenal (MP) in quantitative yields.

Licencja otwartego dostępu

CC-BY

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Pełny tekst licencji: https://creativecommons.org/licenses/by/3.0/pl/legalcode

Adres publiczny

http://dx.doi.org/10.1039/c3dt50992c

Strona internetowa wydawcy

https://www.rsc.org/

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Lasri J., Fernández Rodríguez M. J., Guedes da Silva M. Fátima. C., Smoleński Piotr, Kopylovich Maximilian N., Fraústo da Silva J. J. R., Pombeiro Armando J. L.